Aminophenyl carbamates



United States Patent 3,084,098 AMINOPHENYL CARBAMATES Alexander T. Shulgin, Berkeley, Calif., assignmto The Dow Chemical Company, Midland, Mich, a corporation of Delaware No Drawing. Original application Nov. 4, 1959, Ser. No. 850,779. Divided and this application Aug. 7, 1961, Ser. No. 131,959

19 Claims. (Cl. 167-30) This invention is directed to carharnate compounds, more particularly to certain m-alkyl-substituted p-aminophenyl and p-alkylaminophenyl methylcarbamates represented by the formulas OCONHCH; OCONHCII;

and

0 C ONH on;

and their hydrochloride salts. In this and succeeding formulas, R and R are independently selected from the group consisting of methyl and ethyl; R" is selected from the group consisting of hydrogen and methyl, R' and R" are independently selected from the group consisting of hydrogen and alkyl radicals containing from 1 to 5 carbon atoms, inclusive. The invention also relates to methods and compositions for the control of parasitic organisms.

The products of this invention are white or light colored liquids or low-melting solids soluble in solvents such as alcohols, acetone and dimethylformamide and of low solubility in Water. Hydrochloride salts of these compounds are water-soluble and water-stable.

The compounds of the present invention have many biological applications. These compounds are useful as insecticides showing outstanding activity against chewing insects, aphids and mites. They are further adapted to be employed for the systemic control of insects affecting mammals. They are also useful for the control of trash fish, aquatic pests, mites, helminths and microbes.

The p-alkylaminophenyl methylcarbamate compounds having the structures SJCONHCH; (I)CONHCH;

R R' CH(CH;,):

nlkyl alkyl alkyl alkyl 01' CKCONHCH:

N alkyl alkyl 3,084,098 Patented Apr. 2, 1963 wherein the alkyls are same or diiferent may he prepared by the reaction of an appropriate alkylaminophenol having the structure R- R CI'I(CH3)] nlkyl n1 yl alkyl ahiyl /N alkyl myl with methyl isocyanate, CH NCO, to produce the desired compounds.

The p-alkylaminophenyl carbarnate compounds having the structure OOONHCH; OOONIIOHs (RCONHCH,

/N H myl may be prepared by reacting an alkylidene aminophenol alkylldene 01' C m sh i alkylldene alkylidene The p-aminophenyl methylcarbamate compounds having the structure OCONHCH; OCIONHCIII It- R -H 0In i NH: NH:

t woNuoln NH2 may be prepared by reacting an arylidene aminophenol on or! n R i It. I C(Clhh H il arylidene arylidcne it arylldene with methyl isocyanate to produce the intermediate carbamate OOONHCH; OCONHCH:

II II arylidene aryhdcno OCONIICH;

a rylldena and thereafter hydrolyzing the latter in the presence of dilute acid to produce the hydrochloride salt of the desired compounds and aromatic aldehyde by-product. The basic p-aminophenyl methylcarbamate may be obtained from the hydrochloride salt by reacting the hydrochloride with an equivalent amount of alkali.

In a preferred method for carrying out the preparation of the p-dialkylaminophenyl methylcarbamates, the appropriate dialkylaminophenol is reacted with a substantially equimolar proportion of methyl isocyanate in an inert solvent and in the presence of a catalytic amount of tertiary amine. Suitable solvents for carrying out the reaction include dimethylforrnamide, methylene chloride, hexane or triethylamine. Suitable catalysts for the reaction include triethylamine, trimethylamine and pyridine. The reaction takes place in the temperature range of from about 25 to 39 C. After completion of the reaction, the mixture is concentrated by vaporizing the excess solvent and then cooling to precipitate the desired dialkylaminophenyl methylcarbamate product. The latter may be recovered and purified according to conventional procedures.

In a preferred method for carrying out the preparation of p-monoalkylaminophenyl methylcarbamates, the appropriate alkylidene aminophenol is reacted with a substantially equimolar proportion of methyl isocyanate in an inert solvent and in the presence of a catalyst. The conditions for carrying out this step are similar to that set forth above for the preparation of methylcarbamates of p-dialkylaminophenols. The product resulting from these operations is the intermediate alkylidene-aminophenyl methylcarbamate which precipitates in the reaction mixture as a crystalilne solid. The latter is recovered by filtration and then hydrogenated in the presence of palladium on charcoal catalyst in methanol or ethanol solvent at a pressure of from 10 to 50 pounds per square inch and a temperature of from 10 to 75 C., to produce the desired monoalkylphenyl methylcarbamate product. The latter is recovered from the reaction mixture by filtering off the catalyst, pouring the filtrate into water to precipitate the product as an oil or a solid and recovering the product therefrom by conventional procedures.

In the preferred method for carrying out the preparation of p-(unsubstituted-amino)phenyl methylcarbamates, the appropriate arylidene-aminophenol is reacted with a substantially equimolar proportion of methyl isocyanate in an inert solvent and in the presence of a catalyst. The conditions for carrying out this step are similar to those set forth above for the preparation of p-alkylideneaminophenyl methylcarbamates. As a result of these operations, the arylidene-aminophenyl methylcarbamate intermediate precipitates in the reaction mixture as a crystalline solid or oil. The latter is then hydrolyzed in dilute hydrochloric acid to produce the hydrochloride salt of the desired aminophenyl methylcarbamate. The hydrolysis is conveniently carried out by dissolving the intermediate Schitf base in dilute hydrochloric acid and maintaining the mixture in the temperature range of from about 50 to 60 C. for 30 minutes while stirring. The reaction mixture is then filtered or extracted with a waterimmiscible organic solvent to remove the aldehyde byproduct. The hydrochloride salt of the aminophenyl methylcarbamate may be recovered from the aqueous solution by vaporizing oif the water. Alternatively, the filtrate may be neutralized with aqueous alkali to precipitate the desired aminophenyl methylcarbamate product as a White crystalline solid. The latter may then be rer covered by filtration or by extraction with a suitable solvent such as ether and then purified if desired according to conventional procedures.

The hydrochlorides of certain of the aminophenyl methylcarbarnates of the present invention may be obtained as described in the preceding paragraph. However, a more general method of preparation of the hydrochlorides is by contacting the aminophenyl methylcarbamates prepared as previously described with an equivalent amount of dilute hydrochloric acid or hydrogen chloride gas to obtain the desired hydrochloride as a white crystalline solid. By dilute acid is meant a concentration no greater than 1 normal.

The preparation of the reactant p-aminophenols is dependent on the particular aminophenol. The aminophenol containing no alkyl substituents on the amino nitrogen i NH: wherein in this and succeeding formulas Ar-- is may be prepared according to one of the methods outlined below.

(A) Via an azo-coupling method:

(1) An appropriate phenol in aqueous alkaline solution is reacted with diazotized sulfanilic acid in the temperature range of from C. to C. for from 5 minutes to 12 hours to produce an intermediate azo compound as its sodium salt (2) The intermediate sodium salt of the azo compound is reduced by treating with sodium hydrosuliite at a temperature of from about 80 to 90 C. to produce a p-aminophenol.

( 2) The intermediate p-nitroso derivative of the phenol is reduced by (a) Treating with alkaline solution of sodium hydrosulfide over a temperature of from to C. for a period of from about 0.5 to about 4 hours, or (b) Treating with hydrogen with palladium on charcoal catalyst at a pressure of from 10 to 50 pounds per square inch and a temperature of from 10 to 75 C. to produce the desired aminophenol.

IiO-Ar-NO 0! H2, PdC Symmetrically substituted dialkylaminophenols,

6 may be prepared according methods:

(A) The appropriate p-aminophenol prepared as above described is alkyiated with a suitable alkylating agent such as alkyl sulfate in the presence of sodium bicarbonate at a temperature of from about 25 C. to 100 C, for from several minutes to several hours to produce a p-dialkylaminophenol.

(B) The appropriate p-nitrosophenol prepared as above described is reductively alkylated with an aliphatic aldehyde and hydrogen in the presence of sodium acetate and palladium on charcoal catalyst at a temperature of from 10 to C. and a pressure of from 10 to 50 pounds per square inch to produce a p-dialkylaminophenol.

to one of the following may be prepared as follows:

(i) The p-aminophenol prepared as above described is reacted with a substantially equimolar proportion of an aliphatic aldehyde to prepare an intermediate alkylidene aminophenol alkyl'-CHO H N--ArOI-I (2) The intermediate alkylidene aminophenol is hydrogenated over palladium on charcoal at temperatures of from 10 C. to 75 C. and pressures of from 10 to 50 pounds per square inch to produce the desired monoalkylaminophenol PdG a1k 1'-CrI=NAror -In alkyl-OII:NIIAr-OH The unsymmetrically substituted dialkylaminophenols (allryDr (alkyDz may be prepared as follows:

The monoalkylaminophenol prepared as above described is reacted with an appropriate aliphatic aldehyde and hydrogen in the presence of palladium on charcoal catalyst at a temperature of from 10 C. to 75 C. and pressure of from 10 to 50 pounds per square inch produce the desired unsymmetrically substituted dialkylaminophenol.

The following are examples illustrating with specific compounds the preparation of the reactants employed in the present invention.

Exmnple A.Unszzbstituted Amfnophenols Via Azo Coupling, 4-Amiu0-3,5-X vlenol A solution of 37.0 grams (0.54 mole) of sodium nitrite in milliliters of water was added quickly with stirring and cooling to a solution of 95.6 grams (0.55 mole) of sulfanilic acid and 26.5 grams (0.25 mole) of anhydrous sodium carbonate in 500 milliliters of Water. The resulting mixture was then added quickly with stirring to a slurry of 106 milliliters of concentrated hydrochloric acid and 600 grams of shaved ice and the mixture stirred in an ice bath for 20 minutes while maintaining the temperature below 15 C. to produce a slurry of diazotized sulfanilic acid.

61.0 grams (0.50 mole) of 3,5-xylenol was added to a solution of 100 grams of sodium hydroxide in 600 milliliters of water and 400 grams of ice and cooled to C. An additional 100 milliliters of water was added and to the resulting mixture was added the slurry of diazotized sulfanilic acid prepared as above described and the mixture allowed to stand overnight during which time the tem perature of the reaction mixture rose to room temperature. During this period, the sodium salt of the are coupled 3,5-xylenol formed in the reaction mixture and precipitated as a crystalline solid. The reaction mixture was then heated to 55 C. and 230 grams (2.2 moles) of sodium hydrosulfite added gradually thereto while heating was continued until the temperature reached 85 C. An exothermic reaction then occurred increasing the final temperature to 95 C. with the precipitation of the desired 4-amino-3,5-xylenol as a crystalline solid. The melting point of 4-amino-3,5-xylenol was 178-180 C.

Example B.-Unsubstituted Aminophenols Via Reduction of the Nitroso Compound, 4-Amino-3,5-Xylenol 170 milliliters of concentrated hydrochloric acid was added with stirring and cooling to a solution of 24.4 grams (0.20 mole) of 3,5-xylenol and 160 milliliters of ethanol. The resulting mixture was cooled to about 6 C. and over a period of several minutes 22 grams (0.32 mole) of sodium nitrite added thereto. A reaction started to take place immediately with formation of brown color in the reaction mixture and after about one-half hour, precipitation of a green colored solid started to take place. After about 2 hours, the reaction mixture thickened to the point that stirring became ineffective and the mixture was then poured into water to precipitate the 4-nitroso-3,5xy1enol which was then recovered by filtering the resulting aqueous mixture. The precipitate after washing with water and drying was a light brown solid melting at 183 C. with decomposition.

15.1 grams (0.09 mole) of 4-nitroso-3,5-xyleno1 pre pared as above described and 4.0 grams of sodium hydroxide in 75 milliliters of water was added over a period of 45 minutes to a solution of 10.6 grams (0.19 mole) of sodium hydrosulfide and 0.8 gram of sodium hydroxide in milliliters of water at a temperature of 50 C. The reaction mixture was maintained between 45 and 55 C. for 4 hours and thereafter neutralized with about 13 milliliters of concentrated hydrochloric acid, whereupon a solid precipitated. The mixture was then cooled and filtered and the precipitate disoslved in about 100 milliliters of l-norrnal hydrochloric acid at 100 C. The resulting solution was decolorized with charcoal, filtered to remove the charcoal, and the filtrate neutralized to pH of 7.3 to precipitate the desired 4-amino-3,5-xylenol as a light gray solid melting at 175 177 C.

In an alternative preparation, the reduction was carried out with hydrogen over palladium on charcoal. In a representative operation, 15.1 grams (0.09 mole) of 4-nitroso3,5-xylenol and 1 gram of 5 percent palladium on charcoal and methanol solvent were mixed together and subjected to low pressure (50 pounds per square inch) hydrogenation. In two hours, the pressure dropped to 35 pounds per square inch with the consumption of 0.2 mole of hydrogen to produce the 4-amino-3,5-xylenol. The later after recovery by conventional procedures melted at 181-183 C.

Example C.Symmetrical Dialkylamino Phenols, Via Alkylation, 4-Dimethylamina-3,5-Xylen0l 80 grams of sodium bicarbonate and 80 milliliters (0.86 mole) of dimethyl sulfate were added to a solution of 32 grams (0.23 mole) of 4-amino-3,5-xylenol in 117 milliliters of Water. An exothermic reaction took place during which time the temperature of the reaction mixture was maintained between 25 and C. with external cooling. The mixture was then allowed to stand overnight at room temperature whereupon the desired 4-dimethylamino-3,5-xyleno1 precipitated as a white solid. The latter was recovered by filtration, washed with pentane and air-dried to obtain a purified 4-dimethylarnino- 3,5-xylenol melting from to 92 C.

Example D.Symmetrical Dialkylaminophenols Via Reductive Alkylation, 4-Dimethylamina-3,5-Xylenol 15.1 grams (0.09 mole) of 4-nitroso-3,5-xylenol, 2 grams of sodium acetate and 26 milliliters (0.32 mole) of 37 percent aqueous formaldehyde, and 1.0 gram of 5 percent palladium on charcoal were added to 150 milliliters of methanol. This suspension was subjected to low pressure hydrogenation (50 pounds per square inch) whereupon theoretical hydrogen up-take was achieved in about 2 hours. At the end of this period, catalyst was removed by filtration and the solvent vaporized to obtain as residue at 4-dimethylamino-3,5-xylenol melting from 88 to 92 C.

Example E.Alkylidene-Aminophenols, 4-Is0butylideneamino-3,5-Xylen0l 50 grams (0.37 mole) of 4-amino-3,5-xylenol was mixed with 235 milliliters of 50 percent aqueous ethanol and the resulting slurry heated to 50 C. 37 grams (0.51 mole) of isobutyraldehyde was then added with vigorous agitation and the mixing continued for five minutes and the mixture then poured on ice to precipitate the desired 4-isobutylideneamino-3,S-xylenol as a. tan solid. The latter was recovered by filtration, washed with water and recrystallized from hexane to obtain a purified 4-isobutylideneamino-3,5-xylenol melting from 107 to 112 C.

Example F.Unsymmetrical Dialkylaminophenols, 4- (N ormul-Butyl-M ethylam ino) -3,5 -X ylenol 18 grams (0.119 mole) of 4-methylamino-3,5-xylenol, 2 grams of 5 percent palladium on charcoal powder, 2 grams of sodium acetate trihydrate, milliliters of methanol and 18 milliliters (0.2 mole) of normalbutyraldehyde were placed in the glass bomb of a low pressure hydrogenation apparatus. The air space was purged and a hydrogen pressure of 50 pounds per square inch was established. The bomb was shaken whereupon absorption of hydrogen took place and the reaction was complete in about 1 hour, to produce a 4-(normal-butylmethylamino)-3,5-xylenol. The latter 'was recovered from the hydrogenation mixture by removing the catalyst by filtration, dilution of the methanol solution with water, extraction with pentane, vaporization of the pentane to recover the product as residue and purifying by distillation. The purified product was a light amber oil boiling from 115 to 118 C. at 2 millimeters of mercury pressure.

The following examples illustrate the present invention but are not to be construed as limiting.

Example 1 .4-Dimethylamin0-3,5-Xy[yl M ethylcarbamate oGoNHoHl C H3- 0 HI 1 N (C H3) 1 25.5 milliliters (24.6 grams; 0.45 mole) of methyl isocyanate and 5 drops of triethylamine catalyst were added to a solution of 71.5 grams (0.45 mole) of 4-dimethylamino-3,S-dimethyl-phenol (MP. 85 -92 C.) in 500 milliliters of hexane. The mixture was allowed to react at a temperature of about 35 C. for a period of 8 hours and thereafter concentrated by heating on the steam bath to remove most of the hexane. The mixture was then cooled in an ice bath and seeded with crystals obtained from the reaction mixture to precipitate the desired 4-dimethylamino-3,5-dimethylphenyl methylcarbamate product. The latter was recovered by filtration and found to be a crystalline solid melting from 80 C. to 83 C. (The seed crystals employed in this and subsequent examples were obtained in a conventional manner by vaporizing the solvent from a few drops of reaction mixture and scratching.)

Example 2.4-Dimethylamino-3-Ethyl-5-Methyl-Phenyl Methylcarbamate (llc ONHC II;

25.5 milliliters (24.6 grams; 0.45 mole) of methyl isocyanate and drops of triethylamine catalyst were added to a solution of 71.5 grams (0.45 mole) of 4-dimethylamino-3-ethyl-5-methylphenol (MP. 55 -62) in 500 milliliters of hexane, the mixture allowed to react at a temperature of about 35 C. for about 8 hours, concentrated by vaporizing the hexane to obtain 4-dimethylamino-3-ethyl-5-methyl-pheny1 methylcarhamate product as a reddish-gold oily residue. The latter, after purification by treatment with activated charcoal, was a. colorless liquid and had a refractive index R1325 of 1.5202.

Example 3 .4'- Di-N ormal-Butylamino) -3,5 -X ylyl M ethylcarbamaze O CONHC H;

5.5 milliliters (0.097 mole) of methyl isocyanate and 5 drops of triethylamine catalyst were added to a solution of 21 grams (0.085 mole) of 4-di-normal-butylamino- 3,5xylenol in 200 milliliters of pentane and the mixture stirred initially at about 35 C., and allowed to stand over the weekend at room temperature to produce a 4-(di-normal-butylamino)-3,5-xylyl methylcarbamate product. The latter was recovered by cooling to -15 C., filtering oil the precipitated product and washing to obtain soft, fiutly white crystals which melted at 59.560 C.

Example 4.4-Diethylaminc-3,5-Xylyl Methylcarbamale In a similar manner 16 milliliters (0.28 mole) of methyl isocyanate and 5 drops of triethylamine catalyst were added to a solution of 45 grams (0.23 mole) of 4-diethylamino-3,5-xylenol in hexane, and the mixture stirred at about 35 C. for 8 hours to produce a 4-diethylamino-3,5-xylyl methylcarbamate product. The latter was recovered by seeding to precipitate the product, filtering the precipitated product and washing to obtain a white waxy solid melting at 6263 C.

Example 5.-4-DietlzyIamin0-3-Etlzyl-S-lh'ethylphenyl M erhy lcarbamaze In a similar manner, 0.5 milliliter (0.009 mole) of methyl isocyanate and 2 drops of triethylarnine catalyst were added to a solution of 1 gram (0.0048 mole) of 4- diethylamino-3-ethyl-5-methylphenol in 10 milliliters of hexane and the mixture stirred at about 35 C. for 8 hours to produce a 4-diethylamino-3 ethyl-5-methylphenyl methylcarbamate product. The latter was recovered as a viscous oil by vaporizing oil the solvent. The crude product after purification with activated charcoal was a colorless liquid having a refractive index, H of 1.5153.

Example 6.--4- (Di-Normal-Propylamino) -3,5-Xylyl M ethylcarbamate In a similar manner, 1.7 milliliters (0.03 mole) of methyl isocyanate and 5 drops of triethylamine catalyst 10 were added to a solution of 4 grams (0.018 mole) of 4- (di-normalpropylamino)-3,5-xyienol in hexane and the mixture allowed to stand overnight to produce a 4-(dinormal-propylamino)-3,5-xylyl methylcarbamate product. The latter was recovered by seeding to precipitate the product, filtering the precipitated products and washing to obtain a white crystalline solid melting from to 82 C.

Example 7 In reactions carried out in a manner similar to that above described, the following compounds were prepared:

A 4(dimethylamino)-2,3,5-trimethylphenyl methylcarbamate product as white crystals having a melting point of 97 C. by the reaction of 4-(dimethylamino)-2,3,5- trimethylphenol and methyl isocyanate in the presence of triethylamine catalyst.

A 4-(di isobutylamino) 3,5 xylyl methylcarbamate product as white, fiuify needles having a melting point of 95 96 C. by the reaction of 4-(di-secondary-butyL amino)-3,5-xylenol and methyl isocyanate in the presence of triethylamine catalyst.

A 4-(di-normal-arnylamino)-3,5-xylyl methylcarbarnate as a pale yellow oil having a refractive index, n of 1.5033 by the reaction of 4-(di-normal-amylamino)-3,5- xylenol and methyl isocyanate in the presence of triethylamine catalyst.

Example 8 In similar reactions the following compounds are prepared:

4-diisopropylamino-3-ethyl-5-methyl-phenyl methylcarbamate having a molecular weight of 292 by the reaction of 4-diisopropylamino-3-ethyl-5-methylphenol and methyl isocyanate.

4- bis-( Z-methylbutyl amino) -3 -ethyl-5 methyl phenyl methylcarbaniate having a molecular weight of 348 by the reaction of 4-(bis-(2-methylbutyl)amino)-3-ethyl-5-methylphenol and methyl isocyanate.

4-diisoamylamino-3,5-xylyl methylcarbarnate having a molecular weight of 334 by the reaction of 4-diisoamylamino 3,5-xylenol and methyl isocyanate.

Example 9.3-Tertiary-ButyI-4-DimetlzyIaminophenyl M eth ylcarba'mate (iIICONIIClI;

i sls l N on, CH:

In a manner similar to that previously described, 14.3 milliliters (0.25 mole) of methyl isocyanate and 0.5 milliliter of tricthylamine catalyst were added to a solution of 48.3 grams (0.25 mole) of 3-tertiary'butyl-4-dirnethylaminophenol in milliliters of methylene dichloride and 240 milliliters of normal-hexane and the mixture stirred initially at about 35 C. and allowed to stand at room temperature overnight to produce a 3-tertiary-butyl- 4-dimethylaminophenyl methylcarbamate product which precipitated as a crystalline solid. The latter was recovered by filtration, washed with normal-hexane and airdried. The yield of the product melting from 120 to 123 C. was 57.5 grams or 92 percent of theoretical.

Example Ill-3-lropropyl-4-Dimethylaminoplzenyl M ethylcarbamate In a manner similar to that described in Example 9, 4.7 milliliters (0.082 mole) of methyl isocyanate was added at room temperature to a solution of 13 grams (0.073 mole) of 3-isopropyl-4-dimethylaminophenol in 250 milliliters of hexane and 25 milliliters of methylene chloride. To the resulting mixture was added with stirring 5 drops of triethylamine catalyst whereupon the mixture spontaneously warmed to a temperature of about 30 C. The mixture was then allowed to stand at room temperature for about 65 hours and then warmed to evaporate off most of the solvent. To the remaining solution was added pentane to precipitate the desired 3-isopropyl-4-dimethylaminophenyl methylcarbamate product as a white solid. The latter was recovered by filtration and recrystalized from hexane to obtain a purified product melting at 88-90 C.

Example 11 In reactions carried out in a manner similar to that above described the following compounds are prepared:

A 3-tertiary-butyl-4-diethylaminophenyl methylcarbamate product as a White crystalline solid melting at 86- 87 C. by the reaction of 3-tertiary-butyl-4-diethylaminophenol and methyl isocynnate in the presence of triethylamine catalyst.

A 3tertiary-butyl-4-(di-normal-propylamino) phenyl methylcarbamate product as a white solid melting at 8284 C. by the reaction of 3-tertiary-butyl-4-(di-normal-propylamino)-phenol and methyl isocyanate in the presence of triethylamine catalyst.

A 3 tertiary-butyl 4 (di-normal-butylamino)-phenyl methylcarbamate product as a white solid melting from 81 to 83 C. by the reaction of 3-tertiary-butyl-4-(dinormal-butyl-amino) phenol and methyl isocyanate in the presence of triethylarnine catalyst.

3-tertiary-butyl-4-diisopropylaminophenyl methylcarbamate having a molecular weight of 306 by the reaction of 3-tertiary-butyl-4-diisopropylaminophenol and methyl iso cyanate in the presence of triethylamine catalyst.

3 tertiary-butyl-4-diisoamylaminophenyl methylcarbamate having a molecular weight of 362 by the reaction of 3-tertiary=butyl-4-diisoamylarninophenol and methyl isocyanate in the presence of triethylamine catalyst.

Example I2.-4-(Methyl-Normal-Butylamin0 -3,5-Xylyl Methylcarbamate O C ON IICHI 7.4 grams (0.036 mole) of 4-(methyl-normal-butylamino)-3,5-xylenol was dissolved in 50 milliliters of pentane and 2.5 milliliters (0.044 mole) of methy isocyanate and a few drops of triethylamine catalyst added thereto with stirring. The resulting solution Was allowed to stand overnight. The reaction mixture wa then heated at 100 and 1 to 2 millimeters of mercury to remove the solvent and unreacted methyl isocyanate to recover as residue at 4-(methyl-normal-butylamino)-3,5-xylyl methylcarbamate product as a colorless, viscous oil having a refractive index, 12 of 1.5135.

Example 13.4- (Methyl-Iso-Butylamin) -3,5-Xyly[ Methylcarbamale Example I4.4-(Methyl-Normal-Amylamino)-3,5-Xylyl M ethylcarbamnte In a similar manner, 3.0 milliliters (0.053 mole) of methyl isocyanate was reacted with 8.5 grams (0.038 mole) of 4-(methyl-normalamylamino)-3,5-xyenol in pentane solution in the presence of triethylamine catalyst to produce a 4-(methyl-normal-amylamino) 3,5-xylyl methylcarbamate product as a yellow oil having a refractive index, 11 of 1.5100. The yield of the product was 10.5 grams or 98 percent of theoretical.

Example 15.-4-(Ethyl-Iso-Butylamino)-3,5-Xylyl M ethylcarbamate In a manner similar to that previously described 4-(ethyl-iso-butylamino)-3,5-xylyl methylcarbamate having a refractive index, n of 1.5168 was prepared by the reaction of 14 grams (0.063 mole) of 4-ethyl-isobutylamino)-3,5xylenol and 4.5 milliliters (0.080 mole) of methyl isocyanate in the presence of tricthylamine catalyst.

Example I 6 in similar preparations the following methylcarbamates are prepared:

4-(ethyl-isoaznylamino) -3,5-Xylyl methylcarbamate having a molecular weight of 292 by the reaction of 4-(ethylisoamylamino)-3,5-xylenol and methyl isocyanate.

4-(normal-butyl isopropylamino)-3-ethyl-5 methylphenyl methylcarbamate having a molecular Weight of 304 by the reaction of 4-(normal-butyl-isopropylamino)- 3-ethyl-5-methylphenol and methyl isocyanate.

3-tertiary-hutyl-4-(methyl-normal-propylamino)-phenyl methylcarbamate having a molecular weight of 278 by the reaction of 3-tertiary-butyl-4-(methyl-norrnal-propylamino)-phenol and methyl isocyanate.

3 tertiary-butyl 4 (normal butyl-methylamino)- pllenyhmethylcarbamate having a molecular weight of 292 by the reaction of 3-tertiary-butyl-4-(normal-butylmethylamino) phenol and methyl isocyanate.

3-tertiary-butyl4-[normal-amyl-ethylamino) phenylrnethylcarbamate having a molecular weight of 320 by the reaction of 3-tertiary-buty1-4-(normal-amyl-ethylamino)- phenol and methyl isocyanate.

3-tertiary-butyl-4 (secondary-bitty] isopropylamino)- phenyl-methylcarbamate having a molecular Weight of 320 by the reaction of 3-tertiary-butyl-4-(secondary-butylisopropylarnino)phenol and methyl isocyanate.

3-isopropyl 4 (normal butyl-ethylamino)phenylmethylcarbarnate having a molecular weight of 264 by the reaction of 3-isopropyl-4-(methyl-normal-propylamino)- phenol and methyl isocyanate.

3-isopropyl 4 (normal butyl ethylamino)phenylmethylcarbamate having a molecular weight of 292 by the reaction of 3 isopropyl-4 (normal butyl-methylamino)phenol and methyl isocyanate.

3 isopropy1-4 (normal hexyl ethy1amino)phenylmethylcarbamate having a molecular weight of 320 by the reaction of 3-isopropyl-4-(normal-amyl-ethylamino)- phenol and methyl isocyanate.

3 isopropy1-4 (secondary-butyl isopropylamino)- phenyl-methylcarbamate having a molecular weight of 306 by the reaction of 3-isopropyl-4-(secondary-butylisopropyl-amino)phenol and methyl isocyanate.

Example 17.4-A m no-3-Tertiary-Butylphenyl M ethy lcarbamaze I|\TH1 5.3 milliliters (0.094 mole) of methyl isocyanate and 5 drops of triethylamine were added to a solution of 22.0 grams (0.087 mole) of 4-benzylidene-3-tertiary-butylphenol in 30 milliliters of methylene chloride and 100 milliliters of normal hexane. The resulting mixture was warmed to 35 C. and then allowed to stand overnight at room temperature to obtain a 4-benzylideneamino-3- tertiary-butylphenyl methyl-carbamate intermediate as a yellow crystalline solid which precipitated in the reaction mixture. The latter was recovered by filtration and r crystallized from ethanol-water to obtain a purified intermediate product melting from 109 to 111 C.

10 grams (0.032 mole) of the 4-benzylideneamino-3- tertiary-butylphenyl methylcarbamate intermediate prepared as above described was added with stirring to 600 milliliters of 0.5 normal hydrochloric acid held at 5060 C. and maintained at this temperature with continued agitation for 30 minutes. As a result of this operation, a reaction took place with the formation of a 4-amino-3 tertiary-butylphenyl methylcarbamate-hydrochloride having a molecular weight of 222 and benzaldehyde by-product. The reaction mixture which contained some unreacted starting material as a solid was filtered to remove same and the filtrate extracted with diethyl ether to remove the benzaldehyde by-product. The remaining aqueous acid solution was neutralized with about 35 milliliters of 25 percent sodium hydroxide to precipitate the desired 4-amino-3-tcrtiary-butylphenyl methylcarbamate product as a white solid. The latter was recovered by filtration and dried. The melting point of the product was l61162 C.

Example 18.4-Amino-3,5-Xylyl M ethylcarbamate In a manner similar to that described in Example 17, a 4-benzylideneamino-3,5-xylyl methylcarbamate intermediate was prepared from 2.8 milliliters (0.049 mole) of methyl isocyanate and 10.0 grams (0.044 mole) of 4- benzylideneamine-3,S-xylenol in the presence of a few drops of triethylamine catalyst.

1.8 grams (0.0064 mole) of the 4-benzylidenearnino- 3,5-xyly1 methylcarbamate was hydrolyzed in 75 milliliters of 1.0 normal hydrochloric acid in a manner similar to that above described to produce a 4-amino-3,5-xylyl methylcarbamate-hydrochloride having a molecular weight of 194 and benzaldehyde lay-product. The reaction mixture was extracted with diethyl ether, and neutralized with an aqueous solution of sodium bicarbonate to obtain a 4-amino-3,5-xylyl methylcarbamate product as a white solid. After recovery and drying, the product melted at 108 ll0 C.

Example 19 In a manner similar to that set forth in Examples 17 and 18, 4-amino-3-ethyl-S-methylpheuyl methylcarbamate having a molecular weight of 208 is prepared by the reaction of 4-benzylidene-3-ethyl-5-methylphenol and methyl isocyanate to produce the intermediate 4benzylidene-3- ethyl-S-methylphenyl carbamate followed by the hydrolysis of the latter with dilute hydrochloric acid.

Example 20.-4-I so-Buty lam inc-3 ,5 -X yl yl M eth ylcarbamatc ?CONIIOII;

N H H2O 11-43 11,

30 grams (0.157 mole) of 4-iso-butylideneamino-3,5- xylenol and 17 grams (0.30 mole) of methyl isocyanate were reacted in the presence of triethylamine in a manner similar to that previously described.

Six grams (0.024 mole) of 4-iso-butyiideneamino-3,5- xylyl methylearbamate (M.P. 80-83 (3.), 1.5 grams of 5 percent palladium on charcoal powder and 150 milliliters of methanol were placed in the bomb of a low pressure hydrogenation apparatus. The air was purged with hydrogen and an initial pressure of 50 pounds per square inch of hydrogen was established. The shaker was turned on and hydrogen was absorbed immediately to produce a 4-iso-butylamino-3,S-xylyl carbamate product. The theoretical amount of hydrogen was absorbed in about 5 minutes. After an additional 15 minutes, the shaker was stopped and the hydrogen pressure released. The catalyst was filtered oil to produce a colorless filtrate. The solvent was removed by distillation at 50 and 20 millimeters of mercury pressure to recover the product as a white solid residue. The latter after recrystallization from hexane melted from 97 to 99 C.

Example 21 .4-Is0pr0py lam in0-3,5-Xylyl Met/1y lcarbamate One gram (0.0056 mole) of 4-isopropylamino-3,5- xylenol was dissolved in milliliters of methylene chloride and 0.3 milliliter (0.0054 mole) of methyl isocyanate and a few drops of triethylamine catalyst added thereto. The reaction mixture was allowed to stand overnight to produce a 4-is0propylamino-3,5-xylyl methylcarbarnate product. The latter was recovered from the reaction mixture as a white crystalline solid residue. The latter after recrystallization from cycle-hexane melted at from 68 to 74 C. The yield of the product was 1 gram or 75 percent of theoretical. The product had a nitrogen content of 11.86 percent. The theoretical value is 12.01 percent.

Example 22 In preparations carried out as described in Example 20, the following methylcarbamates are prepared:

3 ethyl 5-methyl-4methylaminophenyl methylcarbamate having a molecular weight of 222 by the reaction of 3-ethyl-5-methyl-4-methylideneaminophenol and methyl isocyanate to produce an intermediate 3-ethyl-5-methyl- 4-methylideneaminophenyl rnethylcarbamate followed by hydrogenation of the latter over palladium on charcoal.

4-ethylamino-3,5-xylyl methylcarbamate having a molecular weight of 222 by the reaction of 4-ethylideneamino-3,5-xylenol and methyl isocyanate to produce an intermediate 4-ethylideneamino-3,S-xylyl methylcarbamate followed by hydrogenation of the latter over palladium on charcoal.

4 (2 methylbutylamino)-3,5-xylyl methylcarbamate having a molecular weight of 264 by the reaction of 4- (Z-methylbutylideneamino)-3,5-xylenol and methyl isocyanate to produce an intermediate 4-(2-methylbutylideneamino)-3,5-xylyl methylcarbamate followed by hydrogenation of the latter over palladium on charcoal.

3 tertiary-butyl-4-rnethylaminophenyl methylcarbamate having a molecular weight of 236 by the reaction of 3-tertiary-butyll-methylideneaminophenol and methyl isocyanatc to produce an intermediate 3-tertiary-butyl-4- methylideneaminophenyl methylcarbamate followed by hydrogenation of the latter over palladium on charcoal.

3 tertiary-buty]-4-isopropylaminophenyl methylcarbamate having a molecular weight of 263 by the reaction of 3-tcrtiary-butyl-4-isopropylideneaminophenol and methyl isocyanate to produce an intermediate B-tertiary-butyl- 4-isopropylideneaminophenyl methylcarbamate followed by hydrogenation of the latter over palladium on charcoal.

3-isopropyl-4- normal-butyl amino phenyl methylcarbamate having a molecular weight of 264 by the reaction of 3-isopropyl-4-(normal-butylidenearnino)phenol and methyl isocyanate to produce an intermediate 3-isopropyl-4- (normalbutylideneamino)phenyl methylcarbamate followed by hydrogenation of the latter over paladium on charcoal.

3-isopropyl-4-(normal-amylamino)phenyl mcthylcarbamate having a molecular weight of 278 by the reaction of 3-isopropyl-4-pentylideneaminophenol and methyl isocyanate to produce an intermediate 3-isopropyl-4-pentylideneaminophenyl methyicarbamate followed by bydrogenation of the latter over palladium on charcoal.

1 Eran 1 pic 23 .-3-Terrimy-Buty I-4-Dim ctr'zylam inophcnyl Methylcarbamate-Hydrochloride 2.50 grams (0.01 mole) of 3-tcrtiary-butyl-4-dimethylaminophenol was dissolved in milliliters of 1.0 normal hydrochloric acid to produce a purple solution. The latter was decolorized at room temperature with activated charcoal and the resulting nearly colorless solution was cooled in a round-bottomed flask until frozen on the walls and subjected to reduced pressure to remove the water by sublimation and to recover as residue the desired 3-tertiary-butyl-4-dimethylaminophenyl methylcarbamate-hydrochloride product which after drying at 100 C. melted at 2l922l C. with decomposition.

Example 24 In a similar manner, the following hydrochlorides are prepared:

4-(dimethylamino)-3,5-xylyl methylcarbamate-hydrochloride, molecular weight of 258.5.

3-tertiary-butyl-4-(di-normal-butylamino)-phenyl methylcarbamatehydrochloride, molecular weight of 370.5.

4 (methyl normal-butylamino)-3,5-xylyl methylcarbamate-hydrochloride, molecular weight of 300.5.

4-(secondary-butylamino)-3,5-xylyl methylcarbamate hydrochloride, molecular weight of 285.5.

The compounds of the present invention are useful as parasiticides in a variety of household, industrial and agricultural operations. Thus. they are useful for the control of various water pests such as trash fish, snails and entomostracans. In representative operations for the control of entomostracans, complete controls of Daphnia sp., Cyclops sp. and Eubranchipus were obtained when these aquatic pests in aqueous media were separately exposed to 4-diemthylamino-3,5-xylyl methylcarbamate at a concentration of 1 part by weight per million parts by weight of medium for 24 hours.

They have also been found to be useful in animal husbandry against pests attacking mammals such as ticks and lice. They are further useful for oral or parenteral administration to warm-blooded animals as systemic insecticides for the control of various species of cattle grub, screw-worms and stable flies, as well as for the control of helminths.

They may also be employed for the control of household and industrial pests including house flies, cockroaches and confused flour beetles.

It has been discovered that the new aminophenyl methylcarbamate are extremely effective for the control of many parasitic organisms, particularly those found on the aerial portions of growing plants inclusive of aphids, mites, plant pathogens and insects. These compounds have outstanding activity against chewing type insects as represented by Mexican bean beetle (Epilyachna varivcstis) and southern army worm (Prodcnia eridania). These compounds are effective against chewing type insects at a low concentration heretofore not believed effective with any known insecticide. Compositions comprising the aminophenyl mcthylcarbamates as an active ingredient in association with various carriers, surface active agents and other additaments are very useful for the control of these undesirable pests. It is an advantage of the present invention that compositions containing the compounds may be applied to growing vegetation in amount required for pest control without significant injury to plane foliage.

In carrying out the method of the present invention, the undesirable pests may be controlled by contacting the organism, its habitat, and/or its food prior to ingestion with a parasiticidal amount of the unmodified methylcarbamate product. However, the present method also embraces the employment of a liquid or dust composition containing the toxicant. Such compositions are adapted to be applied to living plants without substantial injury to the foliage thereof. In preparing toxicant compositions, the methylcarbamate product may be modified with one or more of a plurality of additaments including aromatic solvents, petroleum distillates, water liquid carriers, surface active dispersing agents and finely divided inert solids. Depending upon the concentration in the composition of the methylcarbamate product, such augmented compositions are adapted to be employed for the control of undesirable parasites or employed as concentrates and subsequently diluted with additional inert carrier to produce the ultimate treating compositions. In compositions to be employed as concentrates, the toxicant may be present in a concentration of from about 5 to 95 percent by weight.

The exact concentration of the methylcarbamate product employed in a composition for application to the pests, its habitat or food, may vary provided a parasiticidal dosage of toxicant is supplied either on the organism or its environment, or in its food. This dosage of toxicant is primarily dependent upon the susceptibility of a particular organism to the methylcarbamate product. Good results are obtained with liquid compositions containing as little as 1.5 parts by weight per million parts by weight of toxicant to about l-2 percent by weight, although compositions containing as high as percent may be employed. With dusts, good results are obtained with compositions containing from 0.1 to 10 percent or more by weight of toxicant.

In the preparation of dust compositions, the methylcarbamate product may be compounded with any of the finely divided solids such as pyrophyllite, diatomaceous earth, gypsum and the like. In such operations, the finely divided carrier is ground or mixed with the toxicant or wet with a solution of the toxicant in a volatile organic solvent. Similarly, dust compositions containing the methylcarbamate product may be similarly compounded from various of the solid surface active dispersing agents, such as tullers earth, attapulgite and other clays. Depending upon the proportions of ingredients, these dust compositions may be employed as concentrates and subsequently diluted with additional solid surface active dispersing agent or with pyrophyllite, diatomaceous earth, gypsum and the like to obtain the desired amount of active ingredient in a composition adapted to be employed for the control of pests. Also, such concentrate dust compositions may be dispersed in water, with or without the aid of dispersing agents, to form spray mixtures.

Further, the methylcarbamate product or a dust concentrate composition containing such product may be incorporated in intimate mixture with surface active dispersing agents such as ionic and non-ionic emulsifying agents to form spray concentrates. Such concentrates are readily dispersible in liquid carriers to form sprays containing the toxicant in any desired amount. The choice of dispersing agent and amount thereof employed are determned by the ability of the agent to facilitate the dispersion of the concentrate in the liquid carrier to produce the desired spray composition.

Similarly, the methylcarbamate product may be compounded with a suitable water-immiscible organic liquid and surface active dispersing agent to produce emulsifiable liquid concentrates which may be further diluted with water and oil to form spray mixtures in the form of oil-in-water emulsions. In such compositions, the carrier comprises an aqueous emulsion, i.e., a mixture of water-immiscible solvent, emulsifying agent and water. Preferred dispersing agents to be employed in these compositions are oil-soluble and include the non-ionic emulsifiers such as the organic acids, polyoxyethylene derivatives of sorbitan esters, complex ether alcohols and the like. However, oil-soluble ionic emulsifying agents such as mahogany soaps may also be used. Suitable organic liquids to be employed in the compositions include petroleum oils and distillates, toluene, liquid halohydrocarbons and synthetic organic oils.

When operating in accordance with the present invention, the methylcarbamatc product or a composition containing the toxicant may be applied to the pests to be controlled, to their habitat or to their food in any convenient fashion, e.g., by means of hand dusters or sprayers or by simple mixing with the food to beingested by the organisms. Applications to the foliage of plants conveniently may be carried out with power dusters, boom sprayers and spray dusters. In such foliar applitions, the employed compositions should not contain any appreciable amounts of any phyto-toxic diluents. In large scale operations, dusts or low-volume sprays may be applied from an airplane.

The control of parasitic organisms by the administration of the new aminophenyl methylcarbamates is illustrated by the following examples.

Example 25 In separate operations, concentrate compositions of aminophenyl methylcarbamates having the formulas (KCONHCH; ?CONHCH and oooNHoHl L n R4 nflfl are prepared as follows:

Twenty-five parts by weight of an aminophenyl methylcarbamate, 65 parts of Xylene and parts of an alkylated aryl polyether alcohol are mechanically mixed together to prepare an emulsifiable concentrate composition.

In a similar manner, 90 parts by weight of an aminophenyl methylcarbamate and 10 parts by weight of a sorbitan monolaurate polyoxyethylene derivative (Tween are mixed to prepare a waterdispersible concentrate.

Also, parts by weight of an aminophenyl methylcarbamate, 10 parts of diatomaceous earth, 2 parts of an alkyl aryl sulfonate (Nacconol NR) and 1 part of a polymerized sodium salt of substituted benzoid alkyl sulfonic acids (Daxad No. 27) are mechanically mixed and ground together to prepare a concentrate composition in the form of a wettable powder.

These concentrate compositions are dispersed in water to provide aqueous compositions which have very desirable wetting properties. The latter aqueous compositions are applied to such undesirable pests as aphids, mites, chewing insects, and plant pathogens or to their habitats and food for the control of the organisms.

Example 26 In separate operations, treating compositions containing 4-dimethylamino-3,S-xylyl methylcarbamate, 3-ethyl- 5 methyl 4 dirnethylaminophenyl methylcarbamate, 4- (normal-butyl-methylamino -3,5-xylyl methylcarbamate, 3-tertiary butyl-4-dimethylaminophenyl methylcarbamate and 4-isobutylamino-3,5-xy1yl methylcarbamate were prepared by ballmilling together 0.1 part by weight of the methylcarbamate, 0.15 part of Nacconol NR, 0.15 part of Daxad No. 27 and 500 parts of water. The resulting compositions were further diluted with water to produce aqueous spray treating compositions containing 25 parts per million by weight of one of the methylcarbamates per million parts by weight of ultimate spray mixture. These compositions were separately applied to a series of cran- 18 berry bean plants in amounts sutficient to wet the foliage. The leaf surfaces were then allowed to dry and the plants then infested with a known number of southern army worm (Prodenia eridania) larvae. Three days after infestation, the plants were examined to ascertain the control of southern army worms attributable to the test compounds. It was found that in all cases complete kills of southern army worm larvae were observed.

Those compounds having the structure 0 C ONI-ICIII R!!! RI!!! and their hydrochloride salts are, in addition, useful as antimicrobial agents and are adapted to be employed as toxicant in germicidal and disinfectant compositions. Thus, they may be employed to inhibit the growth of bacteria and fungi as represented by such species as Staphylococcus aureus, Salmonella typhosa, Aerobacrer aerogenes, Erwim'a carotovora, Aspergillus terreus, Pullularia pulfulans, Penicillium digitatum and Rhizopus nigricans. In representative operations for the control of bacteria and fungi, agar medium containing 0.05 percent by weight of 4-dimethylamino-3,S-xylyl methylcarbamate were plated in Petri dishes and in separate operations streaked with S. aureus, E. carolovora, P. pullulans, and P. digitatum and incubated for 3 days at 30 C. Examination of the plates at the end of this period showed complete inhibition of growth of the test organisms.

This application is a divisional application of applicants copending application Serial No. 850,779, now Patent No. 3,060,225.

I claim:

1. A composition comprising an inert parasiticide carrier in admixture with an aminophenyl methylcarbamate selected from the group having the formulas OCONIICH; OGONHCH;

cIIiCIh);

and

oooNrrorr,

R!!! \RIIII wherein R and R are independently selected from the group consisting of methyl and ethyl, R" is selected from the group consisting of hydrogen and methyl, R'" and R"" are independently selected from the group consisting of hydrogen and lower alkyl containing from I to 5 carbon atoms, inclusive, and their hydrochloride salts.

2. A composition claimed in claim 1 wherein the aminophenyl methylcarbamate is present in an amount of at least 1.5 parts by weight per million parts by weight of total composition.

3. A method which comprises applying to insects, their habitats and food a parasiticidal amount of an aminophenyl methylcarbamate selected from the group having the formulas CIKJONIICH, (IJCONHCIIQ u m It It V CH(CIT,;)1

l N N R!!! \RIHI It!!! \IIHI and O C O NH C If;

it R4 \RIIIV O C ONHCII (I)CONHCTI and OCONIICII:

wherein R and R are independently selected from the group consisting of methyl and ethyl, R" is selected from the group consisting of hydrogen and methyl, R' and R" are independently selected from the group consisting of hydrogen and lower alkyl containing from 1 to 5 carbon atoms, inclusive, and their hydrochloride salts.

5. A method according to claim 4 wherein the aminophenyl methylcarbamate is 4-dimethylamino-3,S-xylyl methylcarbamate.

6. A method according to claim 4 wherein the aminophenyl methylcarbarnate is 4-diethylamino-3,5-Xylyl methiylcarbamate.

7. A method according to claim 4 wherein the aminophenyl methylcarbamate is 4-(methyl-normal-butylamino)-3,5-xy1yl methylcarbamate.

8. A method according to claim 4 wherein the aminophenyl methylcarbamate is 4-amino-3-tertiary-butylphenyl methylcarbamate.

9. A method according to claim 4 wherein the aminophenyl methylcarbamate is 4-diethylamino-3-tertiarybutylphenyl methylcarbamate.

10, A method according to claim 4 wherein the aminophenyl methylcarbamate is 4-isobutylamino-3,S-xylyl methylcarbamate.

11. A method according to claim 4 wherein the amino- 2G phenyl methylcarhamate is 4-amino-3,5-xylyl methylcarbamate.

12. A method for controlling pests which comprises applying to the food and feeding areas of said pests, a pest controlling amount of an aminophenyl methylcarbamate selected from the group having the formulas ?GONHCH (BCONHCHs I rr and ?CONHCH3 N R RI!!! wherein R and R are independently selected from the group consisting of methyl and ethyl, R is selected from the group consisting of hydrogen and methyl, R' and R"" are independently selected from the group consisting of hydrogen and lower alkyl containing from 1 to 5 carbon atoms, inclusive, and their hydrochloride salts.

13. A method for controlling pests which comprises applying to food and feeding areas of pests, a pest controlling amount of 4-dimethylaznino-3,5-xylyl methylcarbamate.

14. A pest controlling composition comprising an aminophenyl methylcarbamate selected from th group having the formulas (BCONIICH; ()CONHCH:

R R- R' i CH CH k all I l N N 11!!! \RHII \RIHI and ?CONT{CH I N R!!! \RPIII wherein R and R are independently selected from the group consisting of methyl and ethyl, R is selected from the group consisting of hydrogen and methyl, R' and R" are independently selected from the group consisting of hydrogen and lower alkyl containing from 1 to 5 carbon atoms, inclusive, and their hydrochloride salts, in intimate admixture with a member of the group consisting of surface active dispersing agents, finely divided inert solids and a mixture of a water-immiscible organic liquid and surface active emulsifying agent.

15. A pest control composition comprising 4-dimethylamino-3,5-xyly] methylcarbamate in intimate admixture with a member of the group consisting of surface active dispersing agents, finely divided inert solids and a mixture of a water-immiscible organic liquid and surface active emulsifying agent.

16. In the practice of animal husbandry, a method for controlling parasites attacking warm-blooded animals which comprises administering to the animals a systemic agent comprising an aminophenyl methylcairbamate selected from the group having the formulas (FCONHCHI OOONHCHI R- R w sh 11: N R!!! RVVII RI RIIII and 0 c 0 NH 0 1-1 wherein R and R are independently selected from the group consisting of methyl and ethyl, R" is selected from the group consisting of hydrogen and methyl, R' and R"" are independently selected from the group consisting of hydrogen and lower alkyl containing from 1 to 5 carbon atoms, inclusive, and their hydrochloride salts.

17. A method for controlling parasites attacking warmblooded animals which comprises administering to the animals a parasiticidal amount of 4-dimethylamino-3,5- xylyl methylcarbamate.

18. A composition comprising a systemic agent, said systemic agent being an aminophenyl methylcarbamate selected from the group having the formulas oooNnon. JCONHQH,

nn' carom 40 N N RI, RIIII RI]! RIIII ?CONHOHI and nr Run References Cited in the file of this patent UNITED STATES PATENTS 2,362,508 Stevens et a] Nov. 14, 1944 2,493,710 Aeschlimann et al Jan. 3, 1950 2,843,519 Fitch July 15, 1958 2,854,374 Huismann et a1. Sept. 30, 1958 OTHER REFERENCES Stedman: Biochemical Journal, vol. 20, No. 4, 1926, pp. 719-734.

Kolbezan et al.: I Agr. and Food Chem, vol. 2, No. 17, Aug. 18, 19-54, pp. 8644370, 1954.

Wheatley et al.: I.A.C.S., vol. 79, Feb. 5, 1957, pp. 747-749. 

12. A METHOD FOR CONTROLLING PESTS WHICH COMPRISES APPLYING TO THE FOOD AND FEEDING AREAS OF SAID PESTS, PEST CONTROLLING AMOUNT OF AN AMINOPHENYL METHYLCARBAMATE SELECTED FROM THE GROUP HAVING THE FORMULAS 